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Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b01792· OSTI ID:1469819
 [1];  [2];  [3];  [2];  [3];  [3];  [2];  [3]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; OSTI
  2. Univ. of California, Davis, CA (United States). Dept. of Chemistry
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
+ Show Author Affiliations
Incorporation of Mn into an established water oxidation catalyst based on a Co(III)4O4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo3O4(OAc)5py3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc- ligand for Cl- (1-Cl), NO3- (1-NO3), and pyridine ([1-py]+). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [MnIVCoIII3]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo3O4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.
Research Organization:
Univ. of California, Berkeley, CA (United States)
Sponsoring Organization:
National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; FG02-11ER16282
OSTI ID:
1469819
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Half-sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double-site: Half-sandwich catalysts for water oxidation journal June 2019
Smoothing the single-crystal to single-crystal conversions of a two-dimensional metal–organic framework via the hetero-metal doping of the linear trimetallic secondary building unit journal January 2018
Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoIII2MnII2MnIV2 cluster sustained by a multidentate Schiff base ligand journal January 2019
Heterometallic mixed-valence complex with a {Co II Co III Cu 2 O 4 } core as a new type of cobalt-based oxide cubane journal January 2018

Figures / Tables (11)

Figure 1(p. 14)figure Figure 1
Figure 2(p. 15)figure Figure 2
Figure 3(p. 16)figure Figure 3
Figure 4(p. 17)figure Figure 4
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Figure 8(p. 21)figure Figure 8
Figure 9(p. 22)figure Figure 9
Scheme 1(p. 23)figure Scheme 1
Table 1(p. 24)table Table 1

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